FinFET gate structure and method for fabricating the same

ABSTRACT

A semiconductor device includes a n-type gate structure over a first semiconductor fin, in which the n-type gate structure is fluorine incorporated and includes a n-type work function metal layer overlying the first high-k dielectric layer. The n-type work function metal layer includes a TiAl (titanium aluminum) alloy, in which an atom ratio of Ti (titanium) to Al (aluminum) is in a range substantially from 1 to 3. The semiconductor device further includes a p-type gate structure over a second semiconductor fin, in which the p-type gate structure is fluorine incorporated includes a p-type work function metal layer overlying the second high-k dielectric layer. The p-type work function metal layer includes titanium nitride (TiN), in which an atom ratio of Ti to N (nitrogen) is in a range substantially from 1:0.9 to 1:1.1.

RELATED APPLICATIONS

This application is a divisional of U.S. Nonprovisional patentapplication Ser. No. 15/813,448, titled “FINFET GATE STRUCTURE ANDMETHOD FOR FABRICATING THE SAME” and filed on Nov. 15, 2017, which is acontinuation of U.S. Nonprovisional patent application Ser. No.15/382,478, titled “FINFET GATE STRUCTURE AND METHOD FOR FABRICATING THESAME” and filed on Dec. 16, 2016, which is a continuation in part ofU.S. Nonprovisional patent application Ser. No. 14/983,422, titled“FINFET GATE STRUCTURE AND METHOD FOR FABRICATING THE SAME” and filed onDec. 29, 2015, which claims priority to U.S. Provisional ApplicationSer. No. 62/247,480, titled “3D FINFET METAL GATE SCHEME DESIGN” andfiled Oct. 28, 2015. U.S. Nonprovisional patent application Ser. No.15/813,448, U.S. Nonprovisional patent application Ser. No. 15/382,478,U.S. Nonprovisional patent application Ser. No. 14/983,422, U.S.Provisional Application Ser. No. 62/247,480 are herein incorporated byreference.

BACKGROUND

The semiconductor integrated circuit (IC) industry has experienced rapidgrowth. In the course of the IC evolution, functional density (definedas the number of interconnected devices per chip area) has generallyincreased while geometry size (i.e., the smallest component (or line)that can be created using a fabrication process) has decreased. Ascaling down process generally provides benefits by increasingproduction efficiency and lowering associated costs. But, such scalingdown has increased the complexity of processing and manufacturing ICs.For these advances to be realized, similar developments in ICmanufacturing are needed.

As the semiconductor IC industry has progressed into nanometertechnology process nodes in pursuit of higher device density, higherperformance, and lower costs, challenges from both fabrication anddesign have resulted in the development of three-dimensional (3D)devices such fin-like field effect transistors (FinFETs). Advantages ofFinFET devices include reducing the short channel effect and highercurrent flow. There has been a desire to use a FinFET device with ahigh-k gate dielectric and metal gate electrode to improve deviceperformance as feature sizes continue to decrease. A n-type MOS (NMOS)device and a p-type MOS (PMOS) device require different work functionsfor their respective gate structures. Conventional FinFET devices withhigh-k metal gates and methods of fabricating the FinFET devices havenot been entirely satisfactory in all respects, especially forfabricating a NMOS device together with a PMOS device.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIG. 1 is a schematic cross-sectional view of a semiconductor device inaccordance with some embodiments of the present disclosure.

FIG. 2A and FIG. 2B are schematic cross-sectional views of asemiconductor device in accordance with certain embodiments of thepresent disclosure.

FIG. 3A to FIG. 3G are schematic cross-sectional views of intermediatestages showing a method for fabricating a semiconductor device inaccordance with some embodiments of the present disclosure.

FIG. 4 is a flow chart showing a method for fabricating a semiconductordevice in accordance with some embodiments of the present disclosure.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, orexamples, for implementing different features of the provided subjectmatter. Specific examples of components and arrangements are describedbelow to simplify the present disclosure. These are, of course, merelyexamples and are not intended to be limiting. For example, the formationof a first feature over or on a second feature in the description thatfollows may include embodiments in which the first and second featuresare formed in direct contact, and may also include embodiments in whichadditional features may be formed between the first and second features,such that the first and second features may not be in direct contact.

Terms used herein are only used to describe the specific embodiments,which are not used to limit the claims appended herewith. For example,unless limited otherwise, the term “one” or “the” of the single form mayalso represent the plural form. In addition, the present disclosure mayrepeat reference numerals and/or letters in the various examples. Thisrepetition is for the purpose of simplicity and clarity and does not initself dictate a relationship between the various embodiments and/orconfigurations discussed. The spatially relative terms are intended toencompass different orientations of the device in use or operation inaddition to the orientation depicted in the figures. The device may beotherwise oriented (rotated 90 degrees or at other orientations) and thespatially relative descriptors used herein may likewise be interpretedaccordingly.

It will be understood that, although the terms “first”, “second”,“third”, etc., may be used in the claims to describe various elements,these elements should not be limited by these terms, and these elementscorrespondingly described in the embodiments are presented by differentreference numbers. These terms are used to distinguish one element fromanother. For example, a first element could be termed a second element,and, similarly, a second element could be termed a first element,without departing from the scope of the embodiments. As used herein, theterm “and/or” includes any and all combinations of one or more of theassociated listed items.

Embodiments of the present disclosure are directed to a semiconductordevice on which a PMOS FinFET device and a NMOS FinFET device with metalgate structures are simultaneously formed, thereby simplifying thefabrication process. From an EDS (Energy dispersive spectroscopy)analysis, the NMOS FinFET device includes a n-type work function metallayer. The n-type work function metal layer includes a TiAl (titaniumaluminum) alloy, in which an atom ratio of Ti (titanium) to Al(aluminum) is in a range substantially from 1 to 3, and both surfaces ofthe n-type work function metal layer contains an oxygen concentrationsubstantially less than 10 atom percent (at %). The PMOS FinFET device ap-type work function metal layer overlying the second high-k dielectriclayer. The p-type work function metal layer includes titanium nitride(TiN), in which an atom ratio of Ti to N (nitrogen) is in a rangesubstantially from 1:0.9 to 1:1.1, and the p-type work function metallayer contains an oxygen concentration less than 10 atom percent (at %).Oxygen can cause a shift in the work function of the work function metallayer, and thus less oxygen concentration can lead to the better qualityof the work function metal layer. Therefore, embodiments of the presentdisclosure provide work function metal layers with excellent properties.

Fluorine is a candidate for improving the overall reliability of theHKMG (High-k/Metal Gate) stack by decreasing the BTI (bias-temperatureinstability) threshold voltage shift as well as the SILC (Stress inducedleakage current). For example, fluorine incorporated in High-k (ex.HfO₂) should be able to substitute the missing oxygen at vacancy sites,which results in a more stable bond. It is noted that from the elementalanalysis by the EDS that, the aforementioned compositions, atom ratiosand oxygen and fluorine concentrations are critical. In addition, thehigher fluorine concentration will result in the penalty of devicedrift, and too low fluorine concentration will result in less benefit todevice performance.

Referring to FIG. 1, FIG. 1 is a schematic cross-sectional diagram of asemiconductor device in accordance with some embodiments of the presentdisclosure. The semiconductor device includes a semiconductor substrate102, a semiconductor fin 110 a, a second semiconductor fin 110 b, an-type gate structure 100 a and a p-type gate structure 100 b. Then-type gate structure 100 a and/or the p-type gate structure 100 bare/is fluorine incorporated. The semiconductor fin 110 a and thesemiconductor fin 110 b are disposed on the semiconductor substrate 102,and separated by an isolation structure 104. In some embodiments, theisolation structure 104 is a shallow trench isolation (STI). Thesemiconductor substrate 102 is defined as any construction includingsemiconductor materials, including, but is not limited to, bulk silicon,a semiconductor wafer, or a silicon germanium substrate. Othersemiconductor materials including group III, group IV, and group Velements may also be used. The semiconductor fins 110 a and 110 bprotrude from the semiconductor substrate 102. A gate spacer 122 a isformed on sidewalls of the n-type gate structure 100 a, and a gatespacer 122 b is formed on sidewalls of the p-type gate structure 100 b.The gate spacer 122 a, and the gate spacer 122 b may include siliconoxide, silicon nitride, silicon oxynitride, or other dielectricmaterial. Source/drain portions 112 a and 114 a are disposed on thesemiconductor fin 110 a adjacent to both sides of the gate spacer 122 a,and thus the source/drain portions 112 a and 114 a together with then-type gate structure 100 a forms a NMOS FinFET device. Source/drainportions 112 b and 114 b are disposed on the semiconductor fin 110 badjacent to both sides of the gate spacer 122 b, and thus thesource/drain portions 112 b and 114 b together with the p-type gatestructure 100 b forms a PMOS FinFET device. In some examples, thesource/drain portions 112 a and 114 a include SiP, and the source/drainportions 112 b and 114 b include SiGe.

In some embodiments, an etching stop layer 120 overlies the gate spacer122 a, the source/drain portions 112 a and 114 a, the isolationstructure 104, the gate spacer 122 b, and the source/drain portions 112b and 114 b. An inter-layer dielectric (ILD) 170 overlies the etchingstop layer 120. The ILD 170 may include silicon oxide, phosphosilicateglass (PSG), borophosphosilicate glass (BPSG), and the like.

The n-type gate structure 100 a includes an initial layer 130 a, ahigh-k dielectric layer 140 a, a capping metal layer 142 a, a barriermetal layer 144 a, a TiN layer 146 a, a n-type work function metal layer148 a, a blocking metal layer 150 a, and a metal filler 160 a. Theinitial layer 130 a is disposed over the semiconductor fin 110 a. Insome examples, the initial layer 130 a includes a silicon oxide layer.The high-k dielectric layer 140 a is disposed over the initial layer 130a, and is enclosed by the gate spacer 122 a. The high-k dielectric layer140 a may have a thickness ranging from about 10 angstroms to about 20angstroms. In some embodiments, the high-k dielectric layer 140 a mayinclude a high-k dielectric such as hafnium oxide (HfO₂) hafnium siliconoxide (HfSiO), hafnium silicon oxynitride (HfSiON), hafnium tantalumoxide (HfTaO), hafnium titanium oxide (HfTiO), hafnium zirconium oxide(HfZrO), or combinations thereof.

The capping metal layer 142 a overlies the high-k dielectric layer 140a, and is disposed between the high-k dielectric layer 140 a and then-type work function metal layer 148 a. The capping metal layer 142 aincludes TiN, and may have a thickness ranging from about 10 angstromsto about 30 angstroms. The barrier metal layer 144 a overlies thecapping metal layer 142 a, and is disposed between the capping metallayer 142 a and the n-type work function metal layer 148 a. The barriermetal layer 144 a includes TaN (tantalum nitride) and may have athickness ranging from about 10 angstroms to about 30 angstroms. The TiNlayer 146 a overlies the barrier metal layer 144 a, and is disposedbetween the barrier metal layer 144 a and the n-type work function metallayer 148 a, and may have a thickness ranging from about 5 angstroms toabout 20 angstroms. The capping metal layer 142 a, the barrier metallayer 144 a, and the TiN layer 146 a are used to prevent impurities fromentering underlying layers. In certain embodiments, only one or more ofthe capping metal layer 142 a, the barrier metal layer 144 a, and theTiN layer 146 a is disposed between the high-k dielectric layer 140 aand the n-type work function metal layer 148 a. It is noted that thesequence of the capping metal layer 142 a, the barrier metal layer 144a, and the TiN layer 146 a may be changed without affecting theirpurposes.

The n-type work function metal layer 148 a overlies the TiN layer 146 aand the high-k dielectric layer 140 a, and may have a thickness rangingfrom about 30 angstroms to about 100 angstroms. The n-type work functionmetal layer 148 a includes a TiAl (titanium aluminum) alloy or a TaAl(tantalum aluminum) alloy, in which both surfaces of the n-type workfunction metal layer 148 a adjoin the TiN layer 146 a and the blockingmetal layer 150 a respectively. From a result of EDS line scan, for then-type work function metal layer 148 a including the TiAl alloy, an atomratio of Ti (titanium) to Al (aluminum) is in a range substantially from1 to 3. For the n-type work function metal layer 148 a including theTiAl alloy or the TaAl alloy, the both surfaces of the n-type workfunction metal layer 148 a contains an oxygen concentration less thanabout 10 atom percent (at %), and Al atom concentrations near or at theboth surfaces of the n-type work function metal layer 148 a are higherthan Al atom concentrations at other portions of the n-type workfunction metal layer 148 a, i.e. more Al segregation near or at the bothsurfaces of the n-type work function metal layer 148 a, therebyproviding the work function metal layer with excellent properties.Oxygen can cause a shift in the work function of the n-type workfunction metal layer 148 a, and thus less oxygen concentration can leadto the better quality of the n-type work function metal layer 148 a.

The blocking metal layer 150 a overlies the n-type work function metallayer 148 a for protecting the n-type work function metal layer 148 a,in which the blocking metal layer 150 a includes TiN, and may have athickness ranging from about 10 angstroms to about 30 angstroms. Themetal filler 160 a fills a trench (not labeled) peripherally enclosed bythe blocking metal layer 150 a, and may have a thickness ranging fromabout 1000 angstroms to about 5000 angstroms. The metal filler 160 a canbe configured to provide an electrical transmission. In someembodiments, the metal filler 160 a may be formed from materials such astungsten, copper or other suitable materials, and/or combinationsthereof. The metal filler 160 a is formed by using a fluorine-containedprecursor, and enclosed by a (first) stacked structure 180 a includingthe high-k dielectric layer 140 a, the capping metal layer 142 a, thebarrier metal layer 144 a, the TiN layer 146 a, the n-type work functionmetal layer 148 a, and the blocking metal layer 150 a, in which from aresult of EDS line scan, a side wall of the stacked structure 180 acontains a fluorine concentration substantially from 5 at % to 20 at %,and a bottom of the stacked structure 180 a contains a fluorineconcentration substantially from 1 at % to 15 at %. If the fluorineconcentration of the side wall of the stacked structure 180 a is morethan about 20 at %, significant device drift would be caused. If thefluorine concentration of the side wall of the stacked structure 180 ais less than about 5 at %, then it would have less benefit to deviceperformance. Similarly, if the fluorine concentration of the bottom ofthe stacked structure 180 a is more than about 15 at %, significantdevice drift would be caused. If the fluorine concentration of thebottom of the stacked structure 180 a is less than about 1 at %, then itwould have less benefit to device performance.

The p-type gate structure 100 b includes an initial layer 130 b, ahigh-k dielectric layer 140 b, a capping metal layer 142 b, a barriermetal layer 144 b, a p-type work function metal layer 146 b, a TiAllayer 148 b a blocking metal layer 150 b, and a metal filler 160 b. Insome embodiments, a TaAl layer may be used to replace the TiAl layer 148b. The initial layer 130 b is disposed over the semiconductor fin 110 b.In some examples, the initial layer 130 b includes a silicon oxidelayer. The high-k dielectric layer 140 b is disposed over the initiallayer 130 b, and is enclosed by the gate spacer 122 b. The high-kdielectric layer 140 b may have a thickness ranging from about 10angstroms to about 20 angstroms. In some embodiments, the high-kdielectric layer 140 a may include a high-k dielectric such as hafniumoxide (HfO₂) hafnium silicon oxide (HfSiO), hafnium silicon oxynitride(HfSiON), hafnium tantalum oxide (HfTaO), hafnium titanium oxide(HfTiO), hafnium zirconium oxide (HfZrO), or combinations thereof.

The capping metal layer 142 b overlies the high-k dielectric layer 140b, and is disposed between the high-k dielectric layer 140 b and thep-type work function metal layer 146 b. The capping metal layer 142 bincludes TiN, and may have a thickness ranging from about 10 angstromsto about 30 angstroms. The barrier metal layer 144 b overlies thecapping metal layer 142 b, and is disposed between the capping metallayer 142 b and the p-type work function metal layer 146 b. The barriermetal layer 144 b includes TaN (tantalum nitride) and may have athickness ranging from about 10 angstroms to about 30 angstroms. Thecapping metal layer 142 b and the barrier metal layer 144 b are used toprevent impurities from entering underlying layers. In certainembodiments, only one or more of the capping metal layer 142 b and thebarrier metal layer 144 b is disposed between the high-k dielectriclayer 140 b and the p-type work function metal layer 146 b. It is notedthat the sequence of the capping metal layer 142 b and the barrier metallayer 144 b may be changed without affecting their purposes.

The p-type work function metal layer 146 b overlies the barrier metallayer 144 b, and may have a thickness ranging from about 5 angstroms toabout 20 angstroms. The p-type work function metal layer 146 b includesTiN, in which from a result of EDS line scan, an atom ratio of Ti to N(nitrogen) is in a range substantially from 1:0.9 to 1:1.1, and thep-type work function metal layer 146 b contains an oxygen concentrationless than about 10 atom percent (at %), thereby providing the workfunction metal layer with excellent properties. Oxygen can cause a shiftin the work function of the p-type work function metal layer 146 b, andthus less oxygen concentration can lead to the better quality of thep-type work function metal layer 146 b.

The TiAl layer 148 b overlies the p-type work function metal layer 146b, and is disposed between the p-type work function metal layer 146 band the blocking metal layer 150 b, and may have a thickness rangingfrom about 30 angstroms to about 100 angstroms. The blocking metal layer150 b overlies the TiAl layer 148 b for protecting the TiAl layer 148 band the p-type work function metal layer 146 b, in which the blockingmetal layer 150 b includes TiN, and may have a thickness ranging fromabout 10 angstroms to about 30 angstroms. The metal filler 160 b fills atrench (not labeled) peripherally enclosed by the blocking metal layer150 b, and may have a thickness ranging from about 1000 angstroms toabout 5000 angstroms. The metal filler 160 b can be configured toprovide an electrical transmission. In some embodiments, the metalfiller 160 b may be formed from materials such as tungsten, copper orother suitable materials, and/or combinations thereof. The metal filler160 b is formed by using a fluorine-contained precursor (for example,tungsten hexafluoride (WF₆)), and enclosed by a (second) stackedstructure 180 b including the high-k dielectric layer 140 b, the cappingmetal layer 142 b, the barrier metal layer 144 b, the TiN layer 146 b,the n-type work function metal layer 148 b, and the blocking metal layer150 b, in which from a result of EDS line scan, a side wall of thestacked structure 180 b contains a fluorine concentration substantiallyfrom 5 at % to 20 at %, and a bottom of the stacked structure 180 bcontains a fluorine concentration substantially from 1 at % to 15 at %.If the fluorine concentration of the side wall of the stacked structure180 b is more than about 20 at %, significant device drift would becaused. If the fluorine concentration of the side wall of the stackedstructure 180 b is less than about 5 at %, then it would have lessbenefit to device performance. Similarly, if the fluorine concentrationof the bottom of the stacked structure 180 b is more than about 15 at %,significant device drift would be caused. If the fluorine concentrationof the bottom of the stacked structure 180 b is less than about 1 at %,then it would have less benefit to device performance.

The aforementioned high-k dielectric layers 140 a and 140 b may beformed from one identical layer; the aforementioned capping metal layers142 a and 142 b may be formed from one identical layer; theaforementioned barrier metal layers 144 a and 144 b may be formed fromone identical layer; the aforementioned TiN layer 146 a and p-type workfunction metal layer 146 b may be formed from one identical layer; theaforementioned n-type work function metal layer 148 a and TiAl layer 148b may be formed from one identical layer; the aforementioned blockingmetal layers 150 a and 150 b may be formed from one identical layer; andthe aforementioned metal fillers 160 a and 160 b may be formed from oneidentical layer.

Referring to FIG. 2A and FIG. 2B, FIG. 2A and FIG. 2B are schematiccross-sectional views of a semiconductor device in accordance withcertain embodiments of the present disclosure. The semiconductor deviceincludes a semiconductor substrate 202, a semiconductor fin 210 a, asecond semiconductor fin 210 b, a n-type gate structure 200 a and ap-type gate structure 200 b. The semiconductor fin 210 a and thesemiconductor fin 210 b are disposed on the semiconductor substrate 202,and separated by an isolation structure 204. In some embodiments, theisolation structure 204 is a shallow trench isolation (STI). Thesemiconductor substrate 202 is defined as any construction includingsemiconductor materials, including, but is not limited to, bulk silicon,a semiconductor wafer, or a silicon germanium substrate. Othersemiconductor materials including group III, group IV, and group Velements may also be used. The semiconductor fins 210 a and 210 bprotrude from the semiconductor substrate 202. A gate spacer 222 a isformed on sidewalls of the n-type gate structure 200 a, and a gatespacer 222 b is formed on sidewalls of the p-type gate structure 200 b.The gate spacer 222 a, and the gate spacer 222 b may include siliconoxide, silicon nitride, silicon oxynitride, or other dielectricmaterial. Source/drain portions 212 a and 214 a are disposed on thesemiconductor fin 210 a adjacent to both sides of the gate spacer 222 a,and thus the source/drain portions 212 a and 214 a together with then-type gate structure 200 a forms a NMOS FinFET device. Source/drainportions 212 b and 214 b are disposed on the semiconductor fin 210 badjacent to both sides of the gate spacer 222 b, and thus thesource/drain portions 212 b and 214 b together with the p-type gatestructure 200 b forms a PMOS FinFET device. In some examples, thesource/drain portions 212 a and 214 a include SiP, and the source/drainportions 212 b and 214 b include SiGe.

In some embodiments, an etching stop layer 220 overlies the gate spacer222 a, the source/drain portions 212 a and 214 a, the isolationstructure 204, the gate spacer 222 b, and the source/drain portions 212b and 214 b. An inter-layer dielectric (ILD) 270 overlies the etchingstop layer 220. The ILD 270 may include silicon oxide, phosphosilicateglass (PSG), borophosphosilicate glass (BPSG), and the like.

The n-type gate structure 200 a includes an initial layer 230 a enclosedby a gate spacer 222 a, and the p-type gate structure 200 b includes aninitial layer 230 b enclosed by a gate spacer 222 b. Each of the n-typegate structure 200 a and the p-type gate structure 200 b includes aninitial layer 230 a, a high-k dielectric layer 240, a TiN layer 242, aTaN layer 244, a TiN layer 246, a TiAl layer 248, a TiN layer 250, and ametal filler 260. The initial layer 230 a is disposed over thesemiconductor fin 210 a, and the initial layer 230 b is disposed overthe semiconductor fin 210 b. In some examples, each of the initial layer230 a and the initial layer 230 b includes a silicon oxide layer. Thehigh-k dielectric layer 240 is disposed over the initial layers 230 aand 230 b. The high-k dielectric layer 240 may have a thickness rangingfrom about 10 angstroms to about 20 angstroms. In some embodiments, thehigh-k dielectric layer 140 a may include a high-k dielectric such ashafnium oxide (HfO₂) hafnium silicon oxide (HfSiO), hafnium siliconoxynitride (HfSiON), hafnium tantalum oxide (HfTaO), hafnium titaniumoxide (HfTiO), hafnium zirconium oxide (HfZrO), or combinations thereof.

The TiN layer 242 overlies the high-k dielectric layer 240, and may havea thickness ranging from about 10 angstroms to about 30 angstroms. TheTaN layer 244 overlies the TiN layer 242, and may have a thicknessranging from about 10 angstroms to about 30 angstroms. The TiN layer 246overlies the TaN layer 244, and may have a thickness ranging from about5 angstroms to about 20 angstroms. The TiN layer 242, and the TaN layer244 are used to prevent impurities from entering underlying layers. Incertain embodiments, only one or more of the TiN layer 242, and the TaNlayer 244 is disposed over the high-k dielectric layer 240. It is notedthat the sequence of the TiN layer 242, and the TaN layer 244 may bechanged without affecting their purposes.

The TiAl layer 248 overlies the TiN layer 246 and the high-k dielectriclayer 240, and may have a thickness ranging from about 30 angstroms toabout 100 angstroms. The TiN layer 250 overlies the TiAl layer 248 forprotecting the underlying layers, and may have a thickness ranging fromabout 10 angstroms to about 30 angstroms. The metal filler 260 fills atrench (not labeled) peripherally enclosed by the TiN layer 250, and mayhave a thickness ranging from about 1000 angstroms to about 5000angstroms. The metal filler 260 is formed by using a fluorine-containedprecursor (for example, WF₆), and enclosed by a stacked structure 280including the high-k dielectric layer 240, the TiN layer 242, the TaNlayer 244, the TiN layer 246, the TiAl layer 248, and the TiN layer 250,in which from a result of EDS line scan, a side wall of the stackedstructure 280 contains a fluorine concentration substantially from 5 at% to 20 at %, and a bottom of the second stacked structure contains afluorine concentration substantially from 1 at % to 15 at %. If thefluorine concentration of the side wall of the stacked structure 280 ismore than about 20 at %, significant device drift would be caused. Ifthe fluorine concentration of the side wall of the stacked structure 280is less than about 5 at %, then it would have less benefit to deviceperformance. Similarly, if the fluorine concentration of the bottom ofthe stacked structure 280 is more than about 15 at %, significant devicedrift would be caused. If the fluorine concentration of the bottom ofthe stacked structure 280 is less than about 1 at %, then it would haveless benefit to device performance. The metal filler 260 can beconfigured to provide an electrical transmission. In some embodiments,the metal filler 260 may be formed from materials such as tungsten,copper or other suitable materials, and/or combinations thereof. Achemical mechanical polishing (CMP) operation is performed on the metalfiller 260 shown in FIG. 2A until the gate spacers 222 a and 222 b areexposed, as shown in FIG. 2B. Therefore, a NMOS FinFET device (thesource/drain portions 212 a and 214 a and the n-type gate structure 200a) and a PMOS FinFET device (the source/drain portions 212 b and 214 btogether with the p-type gate structure 200 b) can be simultaneouslyformed, thereby simplifying the fabrication process.

The TiAl layer 248 enclosed by the gate spacer 222 a is a n-type workfunction metal layer, in which both surfaces of the n-type work functionmetal layer adjoin the TiN layer 246 and the TiN layer 250 respectively.From a result of EDS scan line, an atom ratio of Ti (titanium) to Al(aluminum) is in a range substantially from 1 to 3, and the bothsurfaces of the n-type work function metal layer contains an oxygenconcentration substantially less than 10 atom percent (at %), and Alatom concentrations near or at the both surfaces of the n-type workfunction metal layer are higher than Al atom concentrations at otherportions of the n-type work function metal layer, i.e. more Alsegregation near or at the both surfaces of the n-type work functionmetal layer. In some embodiments, a TaAl layer may replace the TiAllayer 248 as the n-type work function metal layer. The TiN layer 246enclosed by the gate spacer 222 b is a p-type work function metal layer,in which an atom ratio of Ti to N (nitrogen) is in a range substantiallyfrom 1:0.9 to 1:1.1, and the p-type work function metal layer containsan oxygen concentration substantially less than 10 atom percent (at %).According to the above EDS features, the work function metal layers withexcellent properties can be provided.

Referring to FIG. 3A to FIG. 3G, FIG. 3A to FIG. 3G are schematiccross-sectional views of intermediate stages showing a method forfabricating a semiconductor device in accordance with some embodimentsof the present disclosure.

As shown in FIG. 3A, a semiconductor substrate 302 is provided, and ispatterned and etched using a photolithography technique to form asemiconductor fin 310 a and a semiconductor fin 310 b which areseparated by an isolation structure 304. The semiconductor substrate 310is defined as any construction including semiconductor materials,including, but is not limited to, bulk silicon, a semiconductor wafer,or a silicon germanium substrate. Other semiconductor materialsincluding group III, group IV, and group V elements may also be used. Insome embodiments, a layer of photoresist material (not shown) isdeposited over the semiconductor substrate 310, and is irradiated(exposed) in accordance with a desired pattern and developed to remove aportion of the photoresist material. The remaining photoresist materialprotects the underlying material from subsequent processing operation,such as etching. It should be noted that other masks, such as an oxideor silicon nitride mask, may also be used in the etching process. Inother embodiments, the semiconductor fin 310 a and the semiconductor fin310 b may be epitaxially grown. For example, exposed portions of anunderlying material, such as an exposed portion of the semiconductorsubstrate 210, may be used in an epitaxial process to form thesemiconductor fin 310 a and the semiconductor fin 310 b. A mask may beused to control the shape of the semiconductor fin 310 a and thesemiconductor fin 310 b during the epitaxial growth process.

A poly gate 380 a is formed on the semiconductor fin 310 a, and a polygate 380 b is formed on the semiconductor fin 310 b. A gate spacer 322 ais formed on sidewalls of the poly gate 380 a, and a gate spacer 322 bis formed on sidewalls of the poly gate 380 b. The gate spacer 322 a,and the gate spacer 322 b may include silicon oxide, silicon nitride,silicon oxynitride, or other dielectric material. Source/drain portions312 a and 314 a are formed on the semiconductor fin 310 a adjacent toboth sides of the gate spacer 322 a. Source/drain portions 312 b and 314b are formed on the semiconductor fin 310 b adjacent to both sides ofthe gate spacer 322 b. In some examples, the source/drain portions 312 aand 314 a include SiP, and the source/drain portions 312 b and 314 binclude SiGe. In some embodiments, an etching stop layer 320 is formedover the gate spacer 322 a, the source/drain portions 312 a and 314 a,the isolation structure 304, the gate spacer 322 b, and the source/drainportions 312 b and 314 b. An inter-layer dielectric (ILD) 370 is formedover the etching stop layer 320. The ILD 370 may include silicon oxide,phosphosilicate glass (PSG), borophosphosilicate glass (BPSG), and thelike.

Thereafter, as shown in FIG. 3B, a portion of the ILD 370 is removed toexpose the etching stop layer 320 by, for example, wet or dry etching.Then, as shown in FIG. 3C, the etching stop layer 320 and the poly gates380 a and 380 b are removed by, for example, wet or dry etching.Thereafter, as shown in FIG. 3D, an initial layer 330 a formed over thesemiconductor fin 310 a, and the initial layer 330 b is formed over thesemiconductor fin 310 b. In some examples, each of the initial layer 330a and the initial layer 330 b includes a silicon oxide layer, may beformed by using chemical vapor deposition (CVD), thermal oxidation,ozone oxidation, other suitable processes.

Then, as shown in FIG. 3E, a high-k dielectric layer 340 is depositedover the initial layers 330 a and 330 b by using atomic layer deposition(ALD) or another suitable technique. The high-k dielectric layer 340 mayhave a thickness ranging from about 10 angstroms to about 20 angstroms.In some embodiments, the high-k dielectric layer 340 may include ahigh-k dielectric such as hafnium oxide (HfO₂) hafnium silicon oxide(HfSiO), hafnium silicon oxynitride (HfSiON), hafnium tantalum oxide(HfTaO), hafnium titanium oxide (HfTiO), hafnium zirconium oxide(HfZrO), or combinations thereof.

A TiN layer 342 is deposited over the high-k dielectric layer 340 byusing ALD or another suitable technique, and may have a thicknessranging from about 10 angstroms to about 30 angstroms. A TaN layer 344is deposited over the TiN layer 342 by using ALD or another suitabletechnique, and may have a thickness ranging from about 10 angstroms toabout 30 angstroms. A TiN layer 346 deposited over the TaN layer 344 byusing ALD or another suitable technique, and may have a thicknessranging from about 5 angstroms to about 20 angstroms. The TiN layer 342,and the TaN layer 344 are used to prevent impurities from enteringunderlying layers. In certain embodiments, only one or more of the TiNlayer 342, and the TaN layer 344 is deposited over the high-k dielectriclayer 340. It is noted that the sequence of the TiN layer 342, and theTaN layer 344 may be changed without affecting their purposes. A TiAllayer 348 deposited over the TiN layer 346 and the high-k dielectriclayer 340 by using ALD or another suitable technique, and may have athickness ranging from about 30 angstroms to about 100 angstroms. Insome embodiments, a TaAl layer may be used to replace the TiAl layer348. A TiN layer 350 formed over the TiAl layer 348 by using ALD oranother suitable technique for protecting the underlying layers, and mayhave a thickness ranging from about 10 angstroms to about 30 angstroms.

Then, as shown in FIG. 3F, a metal filler 360 fills a trench (notlabeled) peripherally enclosed by the TiN layer 350 by using CVD, ALD,Metal-organic Chemical Vapor Deposition (MOCVD), or another suitabletechnique. The metal filler 360 is formed by using a fluorine-containedprecursor (for example, WF₆). The metal filler 360 can be configured toprovide an electrical transmission. In some embodiments, the metalfiller 360 may be formed from materials such as tungsten, copper orother suitable materials, and/or combinations thereof.

Thereafter, as shown in FIG. 3G, a chemical mechanical polishing (CMP)operation is performed on the metal filler 360 until the gate spacers322 a and 322 b are exposed. The metal filler 360 may have a thicknessranging from about 1000 angstroms to about 5000 angstroms Therefore, aNMOS FinFET device (the source/drain portions 312 a and 314 a and then-type gate structure enclosed by the gate spacer 322 a) and a PMOSFinFET device (the source/drain portions 312 b and 314 b and the p-typegate structure enclosed by the gate spacer 322 a) can be simultaneouslyformed, thereby simplifying the fabrication process.

The TiAl layer 348 enclosed by the gate spacer 322 a is a n-type workfunction metal layer, in which both surfaces of the n-type work functionmetal layer adjoin the TiN layer 346 and the TiN layer 350 respectively.From a result of EDS scan line, an atom ratio of Ti (titanium) to Al(aluminum) is in a range substantially from 1 to 3, and the bothsurfaces of the n-type work function metal layer contains an oxygenconcentration substantially less than 10 atom percent (at %), and Alatom concentrations near or at the both surfaces of the TiAl layer 348are higher than Al atom concentrations at other portions of the TiAllayer 348, i.e. more Al segregation near or at the both surfaces of theTiAl layer 348. The TiN layer 346 enclosed by the gate spacer 322 b is ap-type work function metal layer, in which an atom ratio of Ti to N(nitrogen) is in a range substantially from 1:0.9 to 1:1.1, and thep-type work function metal layer contains an oxygen concentrationsubstantially less than 10 atom percent (at %). According to the aboveEDS features, the work function metal layers with excellent propertiescan be provided.

Referring to FIG. 4 and FIG. 3G, FIG. 4 is a flow chart showing a methodfor fabricating a semiconductor device in accordance with someembodiments of the present disclosure. The method begins at operation400, in which a semiconductor fin 310 a (first semiconductor fin) and asemiconductor fin 310 b (second semiconductor fin) are formed on asemiconductor substrate 302, and are separated by an isolation structure304. At operation 410, an initial layer 330 a (first initial layer)enclosed by a gate spacer 322 a (first gate spacer) is formed over thesemiconductor fin 310 a, and an initial layer 330 b (second initiallayer) enclosed by a gate spacer 322 a (second gate spacer) is formedover the semiconductor fin 310 b. At operation 420, a high-k dielectriclayer 340 is deposited over the initial layers 330 a and 330 b. Atoperation 430, a TiN layer 342 (first TiN layer) is deposited over thehigh-k dielectric layer 340. At operation 440, a TaN layer 344 overlyingthe TiN layer 342. At operation 450, a TiN layer 346 (second TiN layer)is deposited over the TaN layer 344. At operation 460, a TiAl layer 348is deposited over the TiN layer 346. At operation 470, a TiN layer 350(third TiN layer) is deposited over the TiAl layer 348. At operation480, a metal filler 360 peripherally enclosed by the TiN layer 350 isdeposited by using a fluorine-contained precursor (for example, WF₆).The metal filler 360 is formed by using a fluorine-contained precursor(for example, WF₆), and enclosed by a stacked structure 390 includingthe high-k dielectric layer 340, the TiN layer 342, the TaN layer 344,the TiN layer 346, the TiAl layer 348, and the TiN layer 350, in whichfrom a result of EDS line scan, a side wall of the stacked structure 390contains a fluorine concentration substantially from 5 at % to 20 at %,and a bottom of the second stacked structure contains a fluorineconcentration substantially from 1 at % to 15 at %. If the fluorineconcentration of the side wall of the stacked structure 390 is more thanabout 20 at %, significant device drift would be caused. If the fluorineconcentration of the side wall of the stacked structure 390 is less thanabout 5 at %, then it would have less benefit to device performance.Similarly, if the fluorine concentration of the bottom of the stackedstructure 390 is more than about 15 at %, significant device drift wouldbe caused. If the fluorine concentration of the bottom of the stackedstructure 390 is less than about 1 at %, then it would have less benefitto device performance.

The TiAl layer 348 enclosed by the gate spacer 322 a acts as a n-typework function metal layer, in which an atom ratio of Ti (titanium) to Al(aluminum) is in a range substantially from 1 to 3, and both surfaces ofthe n-type work function metal layer contains an oxygen concentrationsubstantially less than 10 atom percent (at %), and Al atomconcentrations near or at the both surfaces of the TiAl layer 348 arehigher than Al atom concentrations at other portions of the TiAl layer348, i.e. more Al segregation near or at the both surfaces of the TiAllayer 348. In some embodiments, a TaAl layer may replace the TiAl layer348 as the n-type work function metal layer. The TiN layer 346 enclosedby the gate spacer 322 b acts as a p-type work function metal layer,wherein an atom ratio of Ti to N (nitrogen) is in a range substantiallyfrom 1:0.9 to 1:1.1, and the n-type work function metal layer containsan oxygen concentration substantially less than 10 atom percent (at %).

In accordance with some embodiments, a semiconductor device includes asemiconductor substrate; a first semiconductor fin on the semiconductorsubstrate; a n-type gate structure over the first semiconductor fin. Theblocking metal layer includes TiN (titanium nitride). The n-type gatestructure is fluorine incorporated and includes a first initial layerover the first semiconductor fin; a first high-k dielectric layer overthe first initial layer and enclosed by a first gate spacer; and an-type work function metal layer overlying the first high-k dielectriclayer, the n-type work function metal layer comprising a TiAl (titaniumaluminum) alloy, in which an atom ratio of Ti (titanium) to Al(aluminum) is in a range substantially from 1 to 3; a blocking metallayer overlying the n-type work function metal layer; and a first metalfiller peripherally enclosed by the blocking metal layer, such that thefirst metal filler is enclosed by a first stacked structure, in which aside wall of the first stacked structure contains a fluorineconcentration substantially from 5 atom percent (at %) to 20 at %, and abottom of the first stacked structure contains a fluorine concentrationsubstantially from 1 at % to 15 at %.

In accordance with certain embodiments, a semiconductor device includesa semiconductor substrate; a first semiconductor fin and a secondsemiconductor fin on the semiconductor substrate; a n-type gatestructure; and a p-type gate structure. The first semiconductor fin andthe second semiconductor fin are separated by an isolation structure.The n-type gate structure is fluorine incorporated and includes a firstinitial layer over the first semiconductor fin and enclosed by a firstgate spacer, and the p-type gate structure is fluorine incorporated andincludes a second initial layer over the second semiconductor fin andenclosed by a second gate spacer. Each of the n-type gate structure andthe p-type gate structure includes a high-k dielectric layer over thefirst initial layer and the second initial layer; a first TiN layeroverlying the high-k dielectric layer; a TaN layer overlying the firstTiN layer; a second TiN layer overlying the TaN layer; a TiAl layeroverlying the second TiN layer; a third TiN layer overlying the TiAllayer; and a metal filler peripherally enclosed by the third TiN layer,such that the metal filler is enclosed by a first stacked structure,wherein a side wall of the first stacked structure contains a fluorineconcentration substantially from 5 at % to 20 at %, and a bottom of thefirst stacked structure contains a fluorine concentration substantiallyfrom 1 at % to 15 at %. The TiAl layer enclosed by the first gate spaceris a n-type work function metal layer, in which an atom ratio of Ti(titanium) to Al (aluminum) is in a range substantially from 1 to 3. Thesecond TiN layer enclosed by the second gate spacer is a p-type workfunction metal layer, in which an atom ratio of Ti to N (nitrogen) is ina range substantially from 1:0.9 to 1:1.1.

In accordance with some embodiments, a method includes forming a firstsemiconductor fin and a second semiconductor fin on a semiconductorsubstrate, in which the first semiconductor fin and the secondsemiconductor fin are separated by an isolation structure. A firstinitial layer enclosed by a first gate spacer over the firstsemiconductor fin is formed, and a second initial layer enclosed by asecond gate spacer over the second semiconductor fin is formed. A high-kdielectric layer is deposited over the first initial layer and thesecond initial layer. A first TiN layer is deposited over the high-kdielectric layer. A TaN layer is deposited formed over the first TiNlayer. A second TiN layer is deposited over the TaN layer. A TiAl layeris deposited over the second TiN layer. A third TiN layer is depositedover the TiAl layer. A metal filler peripherally enclosed by the thirdTiN layer is deposited by using a fluorine-contained precursor (such asWF₆). Then, fluorine is diffused to a stacked structure enclosing themetal filler by, for example, performing a thermal process, such that aside wall of the stacked structure contains a fluorine concentrationsubstantially from 5 at % to 20 at %, and a bottom of the stackedstructure contains a fluorine concentration substantially from 1 at % to15 at %. The TiAl layer enclosed by the first gate spacer acts as an-type work function metal layer, in which an atom ratio of Ti(titanium) to Al (aluminum) is in a range substantially from 1 to 3. Thesecond TiN layer enclosed by the second gate spacer acts as a p-typework function metal layer, in which an atom ratio of Ti to N (nitrogen)is in a range substantially from 1:0.9 to 1:1.1.

The foregoing outlines features of several embodiments so that thoseskilled in the art may better understand the aspects of the presentdisclosure. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions, andalterations herein without departing from the spirit and scope of thepresent disclosure.

What is claimed is:
 1. A method for forming a semiconductor device, themethod comprising: forming a first pair of gate spacers; forming ahigh-k dielectric layer in an opening defined between a first gatespacer of the first pair of gate spacers and a second gate spacer of thefirst pair of gate spacers; forming a plurality of metal layers over thehigh-k dielectric layer; and forming a metal filler over the pluralityof metal layers using a fluorine-based precursor, wherein fluorine fromthe fluorine-based precursor diffuses into at least one metal layer ofthe plurality of metal layers.
 2. The method of claim 1, wherein thefluorine-based precursor comprises tungsten hexafluoride.
 3. The methodof claim 1, wherein forming the plurality of metal layers over thehigh-k dielectric layer comprises: forming a first metal layer of theplurality of metal layers over the high-k dielectric layer, wherein: thefirst metal layer comprises Al, and a concentration of Al atoms in afirst edge region of the first metal layer is different than aconcentration of Al atoms in a middle region of the first metal layer.4. The method of claim 3, wherein the first edge region is between themiddle region and the first gate spacer.
 5. The method of claim 3,wherein the middle region is between the first edge region and the firstgate spacer.
 6. The method of claim 3, wherein: the concentration of Alatoms in the first edge region is greater than the concentration of Alatoms in the middle region, a concentration of Al atoms in a second edgeregion of the first metal layer is greater than the concentration of Alatoms in the middle region, and the middle region is between the firstedge region and the second edge region.
 7. The method of claim 1,wherein: the high-k dielectric layer and the plurality of metal layersdefine a stacked structure, and after the fluorine-based precursordiffuses into the at least one metal layer of the plurality of metallayers, a side wall of the stacked structure contains a first fluorineconcentration and a bottom of the stacked structure contains a secondfluorine concentration different than the first fluorine concentration.8. The method of claim 7, wherein the first fluorine concentration isgreater than the second fluorine concentration.
 9. The method of claim7, wherein the first fluorine concentration is substantially from 5 at %to 20 at % and the second fluorine concentration is substantially from 1at % to 15 at %.
 10. The method of claim 1, wherein: forming theplurality of metal layers comprises forming the plurality of metallayers to overlie the first gate spacer, forming the metal fillercomprises forming the metal filler to overlie the first gate spacer, andthe method comprises performing a planarization process to expose thefirst gate spacer after forming the metal filler.
 11. The method ofclaim 1, comprising: forming a second pair of gate spacers; forming adielectric layer between the first pair of gate spacers and the secondpair of gate spacers; and performing a planarization process to remove afirst portion of the dielectric layer, wherein a top surface of a secondportion of the dielectric layer remaining between the first pair of gatespacers and the second pair of gate spacers after the planarizationprocess is concave.
 12. A method for forming a semiconductor device, themethod comprising: forming a first pair of gate spacers; forming aplurality of metal layers in an opening defined between a first gatespacer of the first pair of gate spacers and a second gate spacer of thefirst pair of gate spacers, wherein the plurality of metal layers definea stacked structure; and forming a metal filler over the stackedstructure using a fluorine-based precursor, wherein: the stackedstructure has a first fluorine concentration prior to forming the metalfiller, the stacked structure has a second fluorine concentration afterforming the metal filler, and the second fluorine concentration isgreater than the first fluorine concentration.
 13. The method of claim12, wherein: after forming the metal filler, a concentration of fluorinepresent in a side wall of the stacked structure is different than aconcentration of fluorine present in a bottom of the stacked structure.14. The method of claim 13, wherein the concentration of fluorinepresent in the side wall is substantially from 5 at % to 20 at % and theconcentration of fluorine present in the bottom is substantially from 1at % to 15 at %.
 15. The method of claim 13, wherein the concentrationof fluorine present in the side wall is greater than the concentrationof fluorine present in the bottom.
 16. The method of claim 12, whereinforming the plurality of metal layers comprises: forming a first metallayer of the plurality of metal layers in the opening, wherein: thefirst metal layer comprises Al, and a concentration of Al atoms in afirst edge region of the first metal layer is different than aconcentration of Al atoms in a middle region of the first metal layer.17. The method of claim 16, wherein: the concentration of Al atoms inthe first edge region is greater than the concentration of Al atoms inthe middle region, a concentration of Al atoms in a second edge regionof the first metal layer is greater than the concentration of Al atomsin the middle region, and the middle region is between the first edgeregion and the second edge region.
 18. A method for forming asemiconductor device, the method comprising: forming a first pair ofgate spacers; forming a high-k dielectric layer in an opening definedbetween a first gate spacer of the first pair of gate spacers and asecond gate spacer of the first pair of gate spacers; forming aplurality of metal layers over the high-k dielectric layer; anddiffusing fluorine into at least one metal layer of the plurality ofmetal layers.
 19. The method of claim 18, wherein: the high-k dielectriclayer and the plurality of metal layers define a stacked structure, andafter diffusing the fluorine into the at least one metal layer of theplurality of metal layers, a side wall of the stacked structure containsa first fluorine concentration and a bottom of the stacked structurecontains a second fluorine concentration different than the firstfluorine concentration.
 20. The method of claim 19, wherein the firstfluorine concentration is substantially from 5 at % to 20 at % and thesecond fluorine concentration is substantially from 1 at % to 15 at %.